TW201037030A - Expandable composite resin particles for long-term storage, pre-expanded beads formed therefrom, and molded foam - Google Patents

Abstract

Expandable composite resin particles for long-term storage which comprise a composite resin comprising a polyolefin resin and a polystyrene resin and, incorporated therein, 500-5,000 ppm water and 7.5-11.0 wt.% pentane; pre-expanded beads formed from the particles; and molded foam.

Description

[Technical Field] The present invention relates to a foamable composite resin particle for long-term storage. More specifically, the present invention relates to a foamed composite resin particle for long-term storage of pentane containing a water and a pentane as a volatile foaming agent in a composite resin of a polyolefin resin and a polystyrene resin. . Further, it relates to a preliminary expanded particle obtained by the expandable composite resin particles and a foamed molded article. L· Ίι BACKGROUND OF THE INVENTION In general, foamable particles (also simply referred to as expandable composite resin particles) of a composite resin of a polyolefin resin and a polystyrene resin can be made by using composite resin particles (also referred to as resin particles). ) obtained by impregnating a volatile blowing agent. In addition, in order to improve the moldability of the foamed molded article, it is known that the volatile foaming agent contains water (for example, JP-A-67-146 (see Patent Document 1). The water content of the expandable composite resin particles is from 0.5 to 5% by weight, and the volatile blowing agent used in the examples is butane (n-butane 70%, isobutane 30%). Patent literature

[Patent Document 1: JP-A-6-104746] [Kennechi J 201037030 Summary of the Invention Problems to be Solved by the Invention The volatile foaming agent used in the above-mentioned publication is a calcination. Ding is a gas at normal temperature, but the pentane (10) liquid and other properties are different, pentane will be difficult to obtain a certain quality, usually using butane. In recent years, in many cases, the production site of the expandable composite resin particles is different from the place where the obtained expandable composite resin particles are foamed. In addition, it is necessary to transport the foamable composite resin particles at the same time. However, in order to convey the heat-reducing composite resin particles as the (four) hair-cutting hairs, it is possible to suppress the entanglement to maintain the foamable composite resin particles. It is necessary to transport in the state of foaming ability. Usually, the method used is cold and cold, but contains the case of _expandable composite resin particles. For example, even if it is stored at _15 Torr and is cooled after sufficient cooling, it is considered to be followed by t temperature. From the viewpoint of foaming and safety, it is necessary to use a container that is resistant to pressurization. Therefore, the foamable composite resin particles cannot be transported in a large amount, and there is a problem that the transportation itself costs. On the other hand, when pentane which is a liquid at normal temperature is used as a foaming agent, a container which can be sealed can be used even if the container which is resistant to pressurization of the foamable composite resin particles containing pentane 7 is not refrigerated or cooled. In addition to the bag shape, the safety at the time of preliminary foaming and the foaming ability of the foamable composite resin particles can be sufficiently ensured. However, in the case of refrigerating or cooling the bed for a certain period of time, preliminary foaming is carried out, and the foamed molded article formed by using the preliminary expanded beads may have a problem of poor appearance and a low physical property of 201037030. The bag contains a bag to solve the problem (4) lipid particles. Polyphenylene (IV) According to the present invention, it is possible to provide a type of polyene, a resin and a water atom. Long-term preservation of foaming composite resin pellets

Ο 4外' (4) According to the present invention, it is possible to provide a pre-expanded particle which is prepared by foaming the above-mentioned money storage hair ear tree. According to the present invention, a foam molded body obtained by wedge-forming the preliminary expanded particles can be provided. According to the present invention, the foamable composite resin particles for long-term storage of the present invention can be stored in a conventional sealed container for a long period of time by using the moisture in the two gauges and the pentane as a volatile foaming agent. As a result, the foamable composite resin particles can be transported in a large amount, and the transportation cost can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanned image of a cut surface of a molded body obtained in Example 1. Fig. 2 is a scanned image of a cut surface of the molded body obtained in Example 2. Fig. 3 is a scanned image of a cut surface of a molded body obtained in a comparative example. Fig. 4 is a scanned image of a cut surface of the molded body obtained in Comparative Example 5. Fig. 5 is a graph showing the relationship between the ratio (% by weight) of the polystyrene resin and the absorbance ratio (Α698/Α285〇). In the case of the present invention, the foamable composite resin particles for long-term storage of the present invention are a composite resin of a polyolefin resin and a polystyrene resin, and contain a predetermined amount of moisture. And pentane. Long-term storage means that water and pentane can be maintained within a predetermined range for 72 hours or more when refrigerated or frozen. (Composite Resin Particles) The polyolefin resin system is not particularly limited, and a well-known resin can be used. Further, the polyolefin resin may be crosslinked. For example, branched low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-mercaptomethyl acrylate copolymer, etc. a polyethylene resin such as a crosslinked body of a polymer; and a propylene homopolymer, an ethylene-propylene random copolymer, a propylene-1-butene copolymer, an ethylene-propylene-butylene random copolymer, or the like Polypropylene resin. In the above exemplification, the low density is preferably 0.91 to 0.94 g/cm3, more preferably 0.91 to 0.93 g/cm3. The high density is preferably 0.95 to 0.97 g/cm3, more preferably 0.95 to 0.96 g/cm3. The medium density is the density between the low density and the high density. The polystyrene resin is a copolymer of polystyrene or styrene as a main component and another monomer copolymerizable with styrene. The main component means that styrene occupies 70% by weight or more of the total monomers. As other monomers, α-mercaptostyrene, p-methylstyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, divinylbenzene, and poly are exemplified. Ethylene glycol dimercapto acrylate or the like. In the exemplified, the alkyl group means an alkyl group having 1 to 8 carbon atoms. 201037030 As an olefin-based resin, there are branched low-density polyethylene, linear low-density polyethylene or ethylene-ethylene vinyl acetate copolymer; polystyrene resin is polystyrene, styrene-alkyl acrylate copolymer or A styrene-alkyl methacrylate copolymer is preferred. In the above illustration, the low density is preferably 0.91 to 〇 93 g/cm3.

In the foamable resin particles, the polystyrene resin is contained in an amount of 110 to 730 parts by weight based on 100 parts by weight of the polyolefin resin particles. In addition, the blending amount of the styrene monomer of the raw material of the polystyrene resin is 110 to 730 parts by weight with respect to the content of the polystyrene resin with respect to 1 GG by weight of the material. When the content of the polystyrene resin is more than 73 parts by weight, the crack resistance of the foamed molded article may be low. On the other hand, when it is less than m part by weight, the crack-resistant large towel is increased in degree, but the surface of the foamed foaming resin particles tends to dissipate rapidly. Therefore, there is a case where the bead life of the foamable resin particles is shortened due to the decrease in the retention of the foaming agent. Preferably, the polystyrene resin content is from 120 to 560 parts by weight, more preferably from 14 to 450 parts by weight. The composite grade of polystyrene tree polystyrene_fat means a mixed resin of polystea resin and polyphenylene (10) resin. The mixed resin can be a resin obtained by simply mixing two kinds of resins, and it is preferable to use the poly-modified styrene-butadiene-based resin described below. Preferably, the mixed resin is a polyethylene-modified styrene-based resin.

Mil styrene (tetra) resin (also referred to as modified resin particles) can be obtained by dispersing and maintaining the aqueous material of the material (4), and adding a 201037030 styrene monomer to polymerize it. The method for producing the modified resin particles will be described below. The polyolefin resin particles can be obtained by a known method. For example, the polyolefin resin is melt-extruded by an extruder, and then granulated by cutting or dicing in water to produce polyolefin resin particles. Usually, the shape of the polyene-based resin particles to be used is, for example, a true spherical shape, an elliptical spherical shape (oval shape), a cylindrical shape, a prismatic shape, a pellet shape, or a granular shape. Hereinafter, the polyolefin resin particles are also referred to as micro pellets. The polyolefin resin particles may also contain a radical scavenger. The radical scavenger may be added to the polyolefin resin particles in advance or may be added simultaneously with the extrusion. The radical scavenger is preferably one which has a function of trapping a radical of a polymerization inhibitor (including a polymerization inhibitor), a chain transfer agent, an antioxidant, a hindered amine light stabilizer, and the like, and is difficult to dissolve in water. As the polymerization inhibitor, tert-butylhydroquinone, p-methoxybenzene, 2,4-dihedyl, tert-butyl butyl, second propyl catechin, N-methyl-N- can be exemplified. Nitrosoaniline, N-nitroso-p-hydroxylamine, triphosphoric acid phosphite, ginseng (mercaptophenyl phosphite), linolenic acid triethyl s-(tetra) acid ginseng (2 ethylhexyl) S Tridecane phosphite, decyltridecyl phosphite, diphenyl-(2-ethylhexyl) phthalate, (di)diphenyl-anthracene vinegar, diphenyl benzoate - (13th hospital base) _, benzoic acid dilauric vinegar, tetraphenyl dipropylene glycol diammonium _, tetraphenyl tetra (tridecyl) neopentyl alcohol four Asian vinegar vinegar and other benzene A blocking agent, a sub-polymeric polymerization inhibitor, an aromatic amine-based polymerization inhibitor, a sub-cooling polymerization inhibitor, a side polymerization inhibitor 201037030, and the like. Further, as the chain transfer agent, 2-ethylhexyl hydroperthiopropionate, dipentaerythritol tert-(3-hydrothiopropionate), and ginseng [(3-hydrothiopropylpropane) can be exemplified.醯oxy)-ethyl]isocyanate or the like. As the antioxidant, 2,6-di-tert-butyl-4-methylphenol (BHT), n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyl) can be exemplified. Phenyl)propionate, pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-para (3,5 -di-t-butyl-4-hydroxyphenyl)isocyanate, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl- 4-hydroxyphenyl)benzene, 3,9-bis[2-{3-(3-secondbutyl-4-glycosyl-5-methylphenyl)propanoateoxy}-1,1 -di Mercaptoethyl]-2,4,8,10-tetraoxaspiro[5·5]undecane, distearyl decyl neopentyl glycol diphosphite, ginseng (2,4-di- Tributylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)neopentitol diphosphite, ruthenium (2,4-di-t-butylphenyl) 4 , 4'-Extended biphenyl diphosphonate, bis(2-tert-butyl-4-methylphenyl) neopentyl alcohol diphosphite, 2,4,8,10-tetra-third -6-[3-(3-methyl 4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][l.3.2]dioxaphosphorus, Phenyl-1-naphthylamine, octylated diphenylamine, 4,4-bis(α,α-dibenzyl)diphenylamine, anthracene, Ν'-di-2-naphthyl-p-benzene A phenol-based antioxidant such as a diamine, a phosphoric acid-based antioxidant, or an amine-based antioxidant. As the hindered amine light stabilizer, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl) can be exemplified. 4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4 -Hydroxybenzyl)-2-n-butylmalonate and the like. The amount of the radical scavenger used in 201037030 is preferably 0.005 to 0.5 parts by mass based on 100 parts by weight of the polyolefin resin particles. The polyolefin resin particles may further contain talc, calcium citrate, calcium stearate, synthetic or naturally produced cerium oxide, ethyl bis-stearylamine, methyl acrylate copolymer, and the like. A flame retardant such as a foaming nucleating agent, a hexacyclic ring hexazone*, a triallyl isocyanurate 6 bromine oxide, a coloring agent such as carbon black, iron oxide or graphite, or the like. Subsequently, the pellets are dispersed in an aqueous medium in a polymerization vessel, and the pellets are immersed in a styrene-based monomer to be polymerized. The aqueous medium may, for example, be a mixed medium of water, water and a water-soluble solvent (e.g., an alcohol). As the styrene-based monomer, any of styrene and substituted styrene (the substituent includes a lower alcohol, a halogen atom (particularly a chlorine atom), etc.) can be used. The substituted styrene may, for example, be a chlorostyrene such as chlorostyrene or p-methylstyrene or fluorene-methylstyrene. Among them, styrene is usually preferred. Further, the styrene monomer can use a mixture of styrene and substituted styrene, styrene and a small amount of other monomers capable of copolymerizing (for example, acrylonitrile, alkyl acrylate) (the carbon number of the alkyl moiety is 1) ~8 or so), maleic acid mono- or dialkyl (about 1 to 4 carbon atoms of the alkyl moiety), divinylbenzene, one of ethylene glycol to diacrylic acid or methacrylate, butylene A mixture of an acid anhydride, N-phenyl maleimide, and the like. Of these mixtures, styrene is preferably present in an amount (e.g., 50% by weight or more). Further, a solvent (plasticizer) such as toluene, xylene, cyclohexane, ethyl acetate, dioctyl phthalate or tetrachloroethylene may be added to the styrene monomer. The amount of the styrene-based monomer used is 110 to 730 parts by weight based on 100 parts by weight of the polyolefin-based 10 201037030 resin particles. It is preferably 120 to 560 parts by weight, more preferably 140 to 450 parts by weight. When the amount of the styrene-based monomer used is more than 730 parts by weight, particles of the polystyrene-based resin monomer may be formed without being impregnated with the polyolefin resin particles. Further, there is a case where not only the crack resistance of the foamed molded article is lowered, but also the chemical resistance is lowered. On the other hand, when it is less than 110 parts by weight, the ability to retain the foaming agent of the expandable resin particles may be lowered. When it is low, high foaming becomes difficult. Further, there is a case where the rigidity of the foamed molded body is also lowered. The styrene-based monomer may be impregnated with the polyolefin-based resin particles while being polymerized, or may be carried out before the polymerization is started. Among them, it is preferred to carry out the edge polymerization. In addition, when the polymerization is carried out after the impregnation, the polymerization of the styrene monomer is likely to occur in the vicinity of the surface of the polyanthracene resin particles, and the styrene monomer which is not impregnated in the polyolefin resin particles is produced. In the case of homopolymerization, a large amount of particulate polystyrene resin particles are generated. When the above-mentioned content is calculated by the impregnation of the polycondensate-based resin particles, the polystyrene-based resin and the impregnated styrene-based monomer, and the condensed and polymerized polymer are obtained. A particle composed of a styrene resin. In order to maintain the content of 〇3 to 35 wt%, the styrene monomer can be continuously or intermittently added to the aqueous medium in the polymerization vessel. It is particularly preferable to slowly add a styrene monomer to an aqueous medium. As the polymerization of the styrene monomer, an oil-soluble radical polymerization initiator can be used. As the polymerization initiator, a polymerization initiator which is generally used in the polymerization of the styrene monomer 201037030 can be used. For example, benzoquinone peroxide, laurel osmium peroxide, tert-butyl peroxyoctanoate, third hexyl peroxyoctanoate, tert-butyl peroxybenzoate, and triamyl benzoate may be mentioned. Tert-butyl trimethylacetate, tert-butyl peroxy methacrylate, third hexyl peroxy methacrylate, peroxy-3,3,5-tridecylcyclohexanoic acid Third butyl ester, hexahydroperoxy-p-di-tert-butyl phthalate, 2,2-di-t-butylperoxybutane, di-trihexane peroxide, cyclopentane peroxide, etc. An organic peroxide; an azo compound such as azobisisobutyronitrile or azobisdecyl valeronitrile; and the like. Further, these oil-soluble radical polymerization initiators may be used singly or in combination. As a method of adding a polymerization initiator to a polymerization container, various methods are mentioned. For example, (a) a method in which a polymerization initiator is dissolved in a styrene monomer in a container other than the polymerization vessel, and the styrene monomer is supplied into the polymerization vessel; The agent is dissolved in a solvent such as a part of a styrene monomer or an isoalkane or a plasticizer to prepare a solution. A method in which the solution is supplied to a polymerization vessel simultaneously with a predetermined amount of a styrene monomer; (c) A dispersion obtained by dispersing a polymerization initiator in an aqueous medium. A method in which the dispersion and the styrene monomer are simultaneously supplied into a polymerization vessel. The use ratio of the above polymerization initiator is usually 0.02 to 2.0% by weight based on the total amount of the styrene-based monomer to be added. In the aqueous medium, it is preferred to dissolve the water-soluble radical polymerization inhibitor in advance. Because the water-soluble radical polymerization inhibitor is not only capable of inhibiting the polymerization of styrene-based precursors on the surface of the poly-smoke resin particles, but also preventing the styrene-based monomer in the aqueous medium from floating. Polymerization to reduce the generation of fine particles of a polystyrene resin. As a water-soluble radical polymerization inhibitor, a polymerization inhibitor of lg or more can be used with respect to 100 g of water, and examples thereof include ammonium thiocyanate, zinc thiocyanate, sodium thiocyanate, potassium thiocyanate, and sulfur. Thiocyanate such as aluminum cyanate; sodium sulfoxide, potassium phthalate, ammonium imidate, arginine, silver nitrite, nitrous acid, bismuth nitrite, bismuth citrate, amide Nitrite such as magnesium, acid, dicyclohexammonium nitrite; thioethyl alcohol, monothiopropanediol, thioglycerol, indole acetic acid, mercaptoic acid, thiolactic acid, sulfur malic acid, thioethanolamine, 1, An organic compound containing water-soluble sulfur such as 2-dithioglycerol or 1,3-dithioglycerol, and ascorbic acid, ascorbic acid-acid assay, and the like. Among these, sulphate is particularly preferred. The water-soluble radical polymerization inhibitor is preferably used in an amount of 0.001 to 0.000 parts by weight based on 100 parts by weight of the water of the aqueous medium. Further, it is preferred to add a dispersing agent to the above aqueous medium in advance. Examples of such a dispersing agent include an organic dispersing agent such as partially saponified polyvinyl alcohol, polyacrylate, polyvinyl base (tetra), buffered cellulose, methyl cellulose, magnesium citrate, and hydrazine. An inorganic dispersant such as calcium amide, calcium phosphate, carbon _, acid-filled town, magnesium sulphate or magnesium oxide. Among them, an inorganic dispersant is preferred. ~ μ When using an inorganic dispersant, it is preferred to use a surfactant in combination. Examples of such an interface activity (IV) include, for example, a decyl benzoate, an enedilic acid, and the like. 201037030 The shape and structure of the polymerization container are not particularly limited as long as they have a stirring blade used for suspension polymerization of a styrene monomer. Further, the shape of the stirring blade is not particularly limited, and specific examples thereof include a blade of a v-shaped blade, a Pfaudler leaf, an inclined blade, and a flat blade 'Brumagin leaf. Turbine blades such as turbine blades, fan blades, etc.; such as propeller blades for marine propeller blades. Among these stirring blades, blade is preferred. The agitating leaves may be single-segment leaves or multi-segment leaves. A baffle may also be provided in the polymerization vessel. Further, the temperature of the aqueous medium when the styrene monomer is polymerized in the pellets is not particularly limited, and is preferably in the range of -30 to +20 ° C of the melting point of the polyolefin resin to be used. More specifically, it is preferably 70 to 140 ° C, more preferably 80 to 130 ° C. Further, the temperature of the aqueous medium may be a constant temperature from the start to the end of the polymerization of the styrene monomer, or may be increased stepwise. When the temperature of the aqueous medium is raised, it is preferably increased at a temperature increase rate of 0.1 to 2 ° C /min. Further, when particles composed of a polyolefin resin after crosslinking are used, the crosslinking may be carried out before the styrene monomer is impregnated; or the styrene monomer may be impregnated into the pellets. The polymerization is carried out during the polymerization; or after the styrene monomer is impregnated into the pellets and polymerized. Examples of the crosslinking agent used for crosslinking the polyolefin resin include 2,2-di-tert-butylperoxybutane, dipentane peroxide, and 2,5-diindenyl-2. An organic peroxide such as 5-di-t-butylperoxyhexane. Further, the crosslinking agents may be used alone or in combination of two or more. Further, the crosslinking agent is usually used in an amount of 0.05 to 1.0 part by weight to 14 201037030 parts, based on 100 parts by weight of the polyolefin resin particles (pellets). The method of adding a crosslinking agent is, for example, a method of directly adding a polyolefin-based resin particle; a method of adding a crosslinking agent to a plasticizer or a styrene-based monomer, and adding the crosslinking agent after dispersing the water in the water; , the method of adding. Here, the method of adding the crosslinking agent to the styrene monomer is carried out. According to the above method, the modified resin particles can be obtained. (Amount of Moisture and Pentane) The amount of water contained in the expandable composite resin particles is 500 to 5000 ppm. When the water content is lower than that of the melon, the surface and the internal bubbles in the preliminary foaming will be more than half of the pre-foamed particles, which will cause the bubble deviation to become very large, more than 5 mouthwashes. At 0111, the surface of the preliminary foaming and the preliminary foaming particles which are very coarse at the time of preliminary foaming tend to occupy most of the foamed molded body, and the appearance of the foamed molded article tends to be extremely poor. The preferred moisture content is from 1000 to 4500 ppm. Ethylene can be selected from the group consisting of isovalerone, brothel and a mixture of two kinds of pentacene. It is particularly preferable to use isopentane and n-pentane of pentane in a ratio of 20:80 to 100:?. The amount of pentane contained in the expandable composite resin particles is 7.5 to 11% by weight. When the content ratio of the pentylene is less than 7.5% by weight, the foamability of the expandable composite resin particles may be lowered. When the foaming property is low, it is difficult to obtain a pre-expanded particle having a high volume ratio and a low bulk density, and the foamed molded article obtained by in-mold molding the pre-expanded particle has a low dissolution rate and is resistant to cracking. Sexually low situation. On the other hand, when the weight is more than 11 2010 201037030%, the size of the bubbles in the preliminary expanded particles tends to be too large, and the formability may be lowered, or the strength characteristics such as compression and bending of the obtained foamed molded body may be lowered. The content ratio of pentane is more preferably in the range of 8 - 5 to 10.0% by weight. The foamable composite resin particles containing a predetermined amount of pentane can be obtained by a method of impregnating pentane in an aqueous medium (wet dipping method) or by immersing it in the absence of a medium ( Dry dipping method). The method of adjusting the moisture content of the expandable composite resin particles to a predetermined amount is not particularly limited, and can be adjusted by a known method. For example, when the water content of the composite resin particles is small, the composite resin particles are dispersed in an aqueous medium, and the medium is kept at 100 to 140 ° C for 2 to 5 hours under airtightness to impart moisture to the composite resin particles. Further, it is preferred to add a dispersant in advance in an aqueous medium. When the water content of the composite resin particles is large, the composite resin particles are dried by a dryer to adjust the water content. For example, in a batch type air flow dryer, a predetermined amount of moisture can be adjusted by flowing air of 10 to 70 ° C, more preferably 20 to 60 ° C for 0.5 to 3 hours. Further, the composite resin particles may be contained in a large amount of water and then dried by a dryer to be adjusted. Further, in the environment where the temperature and humidity are controlled to be constant, the composite resin particles may be left for a certain period of time to adjust the moisture content. Further, when the composite resin particles are produced in a large amount, the obtained composite resin particles are air-fed to another container. At this time, by adjusting the air temperature (also referred to as aerodynamic temperature) and the flow rate at the time of air transportation of the composite resin particles, composite resin particles containing a predetermined amount of water can be obtained. For example, it can be easily adjusted to a predetermined temperature by a pneumatic temperature of 10 to 70 ° C, preferably 20 to 60 ° C, and a flow rate of 16 201037030 of 5 to 30 m / sec, preferably 10 to 20 m / sec. The amount of moisture. When the aerodynamic temperature is less than 1 〇 °C, the water content will be greater than 5000 ppm and the aerodynamic temperature will be greater than 70. (: When the water content is less than 500 ppm, on the other hand, when the flow rate is less than 5 m/sec, it may be difficult to transport the composite resin particles in the vertical direction, or the water content may be less than 5 〇〇 ppm. When it is more than 3〇m/sec, although it is not inappropriate, there is a need to make the blower large, and it is uneconomical or the water content is more than 5〇〇ppm. In this way, the moisture content has been adjusted to the specified amount. The composite resin particles are impregnated with a predetermined amount of pentane by a wet impregnation method or a dry impregnation method to obtain a foamable composite resin particle containing a predetermined amount of water and pentane. Then, a method of obtaining the pre-expanded particles and the foamed molded article from the expandable composite resin particles will be described. The foamable composite resin particles are heated by a heating medium such as water vapor as necessary to prepare them. The preliminary expanded particles can be obtained by foaming to a predetermined bulk density. The preliminary expanded particles are preferably 5 to 7 times by volume (bulk density: 0.014 to 0.2 g/cm 3 ). When the multiple is more than 70 times, the independent bubble ratio of the preliminary expanded beads is lowered, and the strength of the foamed molded body obtained by foaming the expandable composite resin particles may be lowered. On the other hand, when the amount is less than 5 times, the weight of the foamed molded article obtained by foaming the expandable composite resin particles may increase. The storage system of the expandable composite resin particles before preliminary foaming Refrigerated or cold 17 201037030 Frozen. Specifically, the system is 5. (In the following, it is preferably -5 ° C or less, more preferably _15 t: or less. Moreover, by filling the mold of the molding machine with the pre-expanded particles, By heating and secondary foaming, the pre-expanded particles are integrally welded, and a foam molded body having a desired shape can be obtained. As the molding machine, it is possible to use a styrene resin-prepared foamed particle. An EPS (Expandable Polystyrene) molding machine or the like used for forming a molded article. The obtained foamed molded article can be used for cushioning materials such as home electric appliances, electronic components, various industrial materials, foods, and the like. For the purpose of transporting containers, etc., it is also suitable to use an impact energy absorbing material such as a core material for a vehicle bumper or a door interior cushioning material. EXAMPLES Hereinafter, the present invention will be further described by way of examples, but the invention is not limited thereto. These examples. <Method for Producing Prepared Expanded Particles> After storage for 168 hours in a cold storage (set at -25 ° C), it was allowed to stand for 1 hour in an environment of room temperature 25 ° C and humidity of 50%. After that, it is pre-expanded by the following conditions: In a normal-pressure preliminary foaming machine (with a volume of 5 〇L) after preheating with steam, 500 to 2000 g of expandable resin particles are charged, and steaming is introduced while stirring. Dry until about 2 MPa is set, and air is also supplied, and it is foamed to a predetermined bulk density (integral multiple) in about 2 to 3 minutes. &lt;In-Mold Molding Condition&gt; The pre-expanded particles were filled in a mold of a molding machine, and steam heating and cooling were carried out using the following conditions, and the foam molded body was taken out from the mold. 18 201037030 Forming Machine: ACE-3SP manufactured by Sekisui Works Co., Ltd. Mold size. 300mm (width) x4〇〇mm (length) x50mm (thickness) Molding conditions Mold heating: 5 seconds Side heating: 5 seconds opposite side heating : 2 〇 second heating on both sides: 20 seconds water cooling: 20 seconds vacuum cooling: setting the vapor pressure at the highest surface pressure of 0_01kgf/cm2 or less: 0.6~1.0kgf/cm2 &lt;volume density and volume multiple of preliminary foamed particles&gt; About 5 g of the preliminary expanded particles (a) were weighed to two decimal places. Subsequently, the weighed preliminary foamed particles are added to a 50 〇cm 3 measuring cylinder having a minimum scale unit of 5 cm 3 , and the pressing device is placed thereon to read the volume (b) of the preliminary expanded particles, which is a ratio of the pressing device. A circular resin plate having a slightly smaller diameter of the measuring cylinder and in which a rod-shaped resin plate having a width of about 1.5 cm and a length of about 3 〇cm is erected and fixed, and the preliminary expanded particles are obtained according to the formula (a)/(b). Bulk density (g/cm3). Further, the reciprocal of the volume multiplication volume density is (b)/(a). &lt;Method for evaluating gas deviation of preliminary expanded particles&gt; The average bubble diameter of the preliminary foamed particles was measured in accordance with the test method of ASTM D2842-69 as follows. 30 pieces of the preliminary foaming particles were prepared by foaming, and 30 pieces of the preliminary foaming particles were taken, and each of them was divided into two by the surface of the core, and a scanning electron microscope (S manufactured by Hitachi, Ltd.) was used. -3000N) Zoom to 15~30 times (according to the situation) to take a 2 section 19 after the 201037030 slice section. The captured images are printed on the A 4 paper, and the length of the straight line and the number of bubbles on the straight line are measured by orthogonally passing the two straight lines passing through the center (the bubbles in contact with the straight line are also measured). As a result of the above, the average chord length (1) of the bubble can be calculated according to the following formula. However, any straight line system should be carried out as much as possible with the bubble not only touching the tangent point. (The number of bubbles included in the contact) The average chord length / line length / (the number of bubbles X magnification) Then, the bubble diameter d = t / 0.616 is calculated according to the following equation, and the arithmetic mean is taken as the average bubble diameter. . Average bubble diameter D (mm) = (bubble diameter n = 1 + bubble diameter n = 2 + · · · + bubble diameter n = 30) / 30 Subsequently, the standard deviation of the average bubble diameter from the deviation of the bubble diameter is calculated (4) The ratio (UXU=S/D) and the bubble deviation degree are evaluated. The value of U is less than 0.5 and is evaluated as ◎, the value of U is Q 5 or more, less than (4) 〇, and the value of the mouth is 0·8 or more. X. &lt;Measurement of water content&gt; 58 composite resin particles or foamable composite resin particles were impregnated into the knitted nails, and the mixture was mixed for 1 minute to replace the moisture on the surface of the particles. Subsequently, the particles were separated by a vacuum filtration apparatus, and methanol was dried and allowed to dry for 5 minutes. Subsequently, the weight of the sample was measured by using a micro-moisture measuring device (AQ-2100 manufactured by Pingluo Co., Ltd.) and using Kaer-Fei Xue at the heating temperature b xuoc (Liu Hong 1)

Fisher's method. 20 201037030 &lt;Measurement of gas content (flavoring agent pentane and butane)> 5 to 20 m g of expandable resin particles are used as measurement samples. The measurement sample was placed in a thermal decomposition furnace (PYR-1A manufactured by Shimadzu Corporation) held at 180 to 200 ° C, and the measurement sample was sealed, and heating was continued for 12 seconds to release the foaming agent. A gas chromatograph (manufactured by Shimadzu Corporation: GC-14B, detector: FID) was used, and a chart of the foaming agent component was obtained under the following conditions. The content (% by weight) of the foaming agent in the expandable resin particles was calculated from the obtained chart based on the calibration curve of the foaming agent component measured in advance. Determination column for gas chromatograph: "Shimalite 60/80NAW" manufactured by Shinwa Chemical Co., Ltd. ((I) 3mmx3m) Column temperature: 70 °C Detector temperature: 110 °C Injection temperature: ll 〇 ° C Carrier gas: nitrogen Carrier gas flow rate: 60 ml/min &lt;Measurement of polystyrene resin ratio&gt; The absorbance ratio (A698/A285〇) was measured in the following manner, and the polystyrene ratio of the preliminary expanded beads or the foamed molded body was measured. . When the foamed particles were prepared, 10 were randomly taken and each was divided into two from the surface by the center using a razor, and the two-section sliced surface was subjected to ATR infrared spectroscopy to obtain an infrared absorption spectrum. In the case of a foamed molded article, one particle is arbitrarily taken from the foamed molded article, and each is divided into two by a center using a razor, and the cross section of the two divided chips is subjected to ATR infrared spectroscopy to obtain an infrared absorption spectrum. Z1 201037030 Here, in the measurement of the center portion of the particle, each of the preliminary expanded beads 2 is equally divided (for example, the preliminary expanded particles having a particle diameter of 5 mm are cut at 25 ± 5 5), and the cross section is closely attached to the ATR edge. mirror. The absorbance ratio (a698/A285〇) was calculated from each of the infrared absorption spectra, and the minimum absorbance ratio and the maximum absorbance ratio were removed. Then, the sum of the remaining _ absorbance ratios is taken as the absorbance ratio (A698/A285〇). The absorbance was measured using a measuring device sold by Nicolet under the trade name "Fourier transform infrared spectrophotometer MAGNA560". Standard samples were obtained according to the following methods. First, a total of 2 g of the present I-based vinyl resin and polyethylene resin (in terms of the ratio to be measured) is used in a combination ratio (poly ◎ 乙 树 树 曰 聚 聚 聚 聚 聚 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰The composite resin particles contain the same composition). Composition ratio (PS/PE: weight ratio): 〇/1〇=only pE resin, 1/9, 2/8, 3/7, 4/6, 5/5, 6/4, 7/3, 8 /2, l〇/〇 = PS The resin was obtained by heating and kneading the resin by a small injection molding machine under the following conditions: a cylindrical sample having a diameter of 25 mm and a height of 2 mm to obtain a standard sample. In addition, as a small injection molding machine, for example, a product sold under the trade name "CS-183" by CSI is used, and it can be molded, for example, under the following conditions. Ejection is liter; J condition: heating temperature 200 to 250 ° C, kneading time 1 〇 minute The standard sample of the above ratio is measured by the above-mentioned measuring device, and the polystyrene resin (% by weight) is compared with the absorbance ratio (A698/ The relationship of A285〇 is graphed to obtain the calibration curve of Fig. 5. In Fig. 5, when the ratio of the polystyrene resin is 3 〇% by weight or less, the calibration curve can be approximated by the following formula (1). 22 201037030 Υ=21.112Χ (1) In Fig. 5, the ratio of the polystyrene resin is 3 〇. /. When the amount is less than 80% by weight, the calibration curve can be approximated by the following formula (2). Y = 28.415Ln(X) + 20.072 (2) Further, when the ratio of the polystyrene resin is 80% by weight or less in the fifth graph, the calibration curve can be approximated by the following formula (3). Y-12.577 Ln(X)+53.32 (3) Further, in the above formula, X represents an absorbance ratio (A698/A285), and Y represents a polystyrene resin ratio. The polystyrene resin ratio (% by weight) of the preliminary expanded beads or the foamed molded article sample can be calculated based on the calibration curve of Fig. 5 . Example 1 a) Production of Polyethylene Modified Phenolic Resin Particles of Polyethylene Resin (ρΕ)/Polystyrene Resin (ps)=3〇/7〇 Ethylene-Ethyl Acetate Copolymerized Resin Particles (made by Japan P〇LY ETHYLENE Co., Ltd., LV_丨丨5), which is heated and mixed by an extruder and pelletized by a water cutting method (the ethylene-vinyl acetate copolymer resin particle system is adjusted to an average of 100 grains of 80 mg). . 10.5 kg of the ethylene-vinyl acetate copolymer resin particles were placed in a 100 L autoclave equipped with a stirrer, and 45 kg of pure water as an aqueous medium, 315 g of magnesium phthalate, and 16 g of sodium dodecane sulfonate were stirred and stirred. It was allowed to suspend in an aqueous medium for 1 minute and then warmed to 60 °C. Subsequently, 4.5 kg of phenylhexene monomer dissolved in 5.4 g of dipentane peroxide was dissolved in the suspension for 30 minutes. After dripping, at 6 〇. 〇 Maintain 201037030 for 30 minutes to allow poly(4-) resin particles to absorb stupid ethylene monomer. After absorption, the temperature is raised to 130. (: 'And continue mixing at this temperature (hours 45 minutes. Then, the temperature is lowered to the thief, and after the liquid is sprayed with the second sodium benzene, the solution is dissolved in 2 hours as a polymerization. 39.4 benzoyl peroxide, 4.9 g of benzoic acid benzoic acid, and 98% of 6.2 kg of styrene monomer as a cross-linking peroxide. Then, it was dissolved in 2 hours. 175 g of ethyl bis-stearylamine formed by 13·8 #styrene monomer. After the end of the dropwise addition, at 9 (TC for 1 hour, then, the temperature was raised to 143 ° C, and maintained at this temperature for 2 hours. Then, the polymerization is completed. Subsequently, it is cooled to room temperature, and the polyethylene-modified styrene-based resin particles are taken out. Further, 'the styrene-based monomer system is brewed with respect to 100 parts by weight of ethylene-vinyl acetate. 233 parts by weight is used b) Water content adjustment The polyethylene modified styrene resin particles obtained as described above are dehydrated using a basket centrifugal separator, and the dehydrated polyethylene modified styrene resin particles are used. Use a cylindrical dryer to dry the air at room temperature for 3 hours to dry. The polyethylene-modified styrene-based resin particles obtained in this manner contained a water content of 583 ppm. c) Impregnation of a foaming agent (wet dipping method) 2 kg of polyethylene-modified benzene obtained as described above The ethylene resin particles were placed in a 5 L autoclave equipped with a stirrer, and 2 kg of pure water as an aqueous medium and 2 g of sodium dodecylbenzenesulfonate were added, stirred and suspended in an aqueous medium for 1 minute, added. 24〇g contains 973⁄4 or more of isopentane pentane (gas species a: manufactured by SK Industries, Inc., product name ISOBUTANE). 24 201037030

After Ik, it was raised to 6 (rc, and stirring was continued at this temperature for 3 hours. Then, it was cooled to the regular fox and the particles were taken out. The foamable composite resin granules obtained as described above had an 8.3 wt% of the uterine content and 660. Water content of the port 111. d) Storage The foamable composite resin particles 8 obtained as described above were each filled in a 2 L aluminum sealed container, and stored in a freezer set to _25 for 168 hours. e) After the above-mentioned storage, the foam is filled in a 2L aluminum closed container, and the package is heated to room temperature with the remaining part of the tree, and placed in an environment of 50% humidity for 1 hour. Under the preliminary foaming conditions, the foaming composite was used to foam the particles at a volume ratio of 5 〇 times, and the preliminary expanded particles having a volume multiple of 50 times were obtained. The obtained preliminary expanded beads were evaluated in accordance with the bubble deviation evaluation method of the preliminary expanded particles described above. The results are summarized in Table 1. f) Foaming molding The pre-expanded particles obtained as described above are stored in an environment of room temperature and humidity of 50%, and then foamed under the above-mentioned in-mold forming conditions to obtain a foam of 50 times. Shaped body. The obtained molded body was cut into 50 x 75 mm', and after the skin was removed by about 5 mm, the surface after peeling off the skin was cut to a thickness of about 1 to 2 positions. The image stored in the 5〇χ75_χ 1~2(1) mm slice is shown in Fig. 1 using a scanner (GT-S600 manufactured by Ep s 〇n Co., Ltd.). 201037030 Example 2 The production of the polyethylene-modified styrene-based sulphate particles was carried out in the same manner as in a) of Example 1, and the water content adjustment was carried out in the same manner as in Example 丨 except that the drying time was hour. In the case of the foaming lion dipping system, in addition to the use of 260 g of 97% or more of the pentylene pentoxide (gas type &amp; : team industry company's product name Ι^ΟΒΙΙΤΑΪΝίΕμχ, and the example i c) (wet type) The immersion method was carried out in the same manner as in the case of d), e) and f) of the first embodiment, and the foamed molded article was obtained in the same manner. The results of various measurements are as shown in Table 1. Further, the same procedure as in Example , was carried out, and the scanned image of the cut surface of the obtained molded body was as shown in Fig. 2 . The ratio of the polystyrene resin in the center portion of the preliminary expanded particles having a volume multiple of 50 was 68% by weight. (Approximate as the ratio of blending). Example 3 a) Production of polyethylene-modified styrene resin particles of polyethylene resin (PE) / polystyrene resin (ps) = 4 〇 / 6 将 ethylene-vinyl acetate copolymerized resin particles (Japanese p〇LY ETHYLENE 5), ΙΛΜΙ5) The (four) job is combined with a water-cutting method to pelletize (the ethylene-vinyl acetate copolymer resin particle system is adjusted to an average of 100 grains of 80 mg). 14 kg of the ethylene-vinyl acetate copolymer resin particles were added to a 100 L autoclave equipped with a stirrer, and 45 ^ was added as a water-based pure water, 315 g of a pro-acid lock, and a 12-decaned sodium sulphate. Stir and allow to suspend in an aqueous medium for 10 minutes, then warm to 60 °C. Subsequently, in the suspension, 6.0 kg of styrene monomer dissolved in 72 g of dipentane peroxide 26 201037030 was added dropwise over 30 minutes. After the dropwise addition, the mixture was kept at 60 ° C for 3 minutes to absorb the styrene monomer by the polyethylene resin particles. After absorption, the temperature was raised to 130 ° C, and stirring was continued at this temperature for 2 hours. Subsequently, the temperature was lowered to 9 〇. (:, and after adding 11.4 g of sodium dodecylbenzenesulfonate base to the suspension, '39.9 g of benzoyl peroxide and 3.2 g of benzoic acid benzoic acid dissolved as a polymerization initiator were added dropwise over 1.5 hours. Butyl ketone and i 〇 2.2 g of 5 kg of styrene monomer as a cross-linking agent of dipentane peroxide. Subsequently, 10 kg of benzene dissolved in 105 g of ethyl bis-stearylamine was dissolved in 0.5 hour. Ethylene monomer. After the completion of the dropwise addition, at 90 ° (: for 1 hour, then, the temperature was raised to 143, and the temperature was maintained for 2.5 hours at the sinus temperature to end the polymerization. Then, it was cooled to normal temperature, and the particles were taken out. With respect to 100 parts by weight of the ethylene-vinyl acetate copolymer resin particles, 150 parts by weight of the styrene system was used. The water content adjustment was carried out in the same manner as in the example coffee, and the impregnation of the foaming agent was carried out except for 28 In the same manner as in the example wc)) (wet impregnation method), the 系g contains 97% or more of the broth (the gas type a: 〇SK Industries, Ltd., product name IS0BUTANE), and the storage system is D) of Example i was carried out in the same manner, and the preliminary foaming system was 30 times in addition to the volume ratio. Example m e) in the same manner into the left foot τ 'based foam molding and foam molding the same manner as in Example just come to the embodiment. The results of various measurements are shown as magic. Example 4 The production of the polyethylene-modified phenylene-based resin particles was carried out in the same manner as in the example (a), and the water content adjustment was carried out in the same manner as in the example b) except that the drying time was 0.5 hours. The impregnation of the foaming agent is in addition to the use of 27 201037030 280 g of pentane containing 97% or more of isopentane (gas type a: 8 inch industrial company, product name ISOBUTANE), and the illusion wet dipping with the example In the same manner as in the example of the example, the preliminary foaming system was carried out in the same manner as in the example 丨, and the foaming molding system and the first embodiment were carried out in the same manner as in the example 丨. F) was carried out in the same manner to obtain a foam molded article. The various measurement results are shown in Table 1. The ratio of the polystyrene resin in the center portion of the preliminary expanded particles having a volume ratio of 30 times was 62% by weight. (Approximate as the ratio of blending). Example 5 The production of the polyethylene-modified styrene-based resin particles was carried out in the same manner as in a) of Example 1, and the water content adjustment was carried out in the same manner as in the example b) except that the drying time was 丨hour. . c) Impregnation of foaming agent (dry impregnation method) 15 kg of polyethylene-modified styrene resin particles obtained as described above and 1950 g of pentane containing 97% or more of isopentane (gas species a : SK Industrial Co., Ltd., product name ISOBUTANE) was added to a 50L V-type mixer and mixed for 10 minutes. It was then raised to 60 ° C and stirring was continued for 3 hours at this temperature. It was then cooled to normal temperature and the particles were taken out. The expandable composite resin particles obtained as described above had a pentane content of 9.2% by weight and a water content of 2178 ppm. Each of the storage, the preliminary foaming, and the foam molding was carried out in the same manner as in the above), d), e), and f), to obtain a foam molded article. The results of various measurements are shown in Table 1. Example 6 28 201037030 The production of the polyethylene-modified styrene-based resin particles was carried out in the same manner as in a) of Example 1, and the water content adjustment system was carried out in the same manner as in the example b). The impregnation system is the same as C) of Example 1 except that 240 g of pentane of n-pentane/isopentane = 75/25 to 85/15 (gas species b: manufactured by COSMO Petroleum Co., Ltd., product name butane) is used. The wet impregnation method was carried out in the same manner, and each of the storage, the preliminary foaming, and the foam molding was carried out in the same manner as in the above), d) and f). The various measurement results are shown in Table 1. Comparative Example 1

The production of the polyethylene-modified styrene-based resin particles was carried out in the same manner as in a) of Example 1, and the water content adjustment was carried out in the same manner as in the b) of Example 1, except that the drying time was 5 hours. The impregnation system is carried out in the same manner as the pentane (gas type a: manufactured by SK Industries Co., Ltd., product name: ISOBUTANE) containing 28% or more of isopentane, and is carried out in the same manner as the (10) impregnation method of the real 丨. The storage, preliminary foaming, and foam molding were carried out in the same manner as in the examples (%) and (e), and the foamed molded article was obtained. The results of various measurements are as shown in Table 1. Further, in the same manner as in the first embodiment, the scanned image of the cut surface of the obtained molded body was as shown in Fig. 3. In Comparative Example 2, the water content adjustment was carried out in the same manner as in Example 1, and the &amp; The various measurement results are shown in Table i. Comparative Example 3: riding resin particles _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the same manner as c) (dry immersion method) of Example 5 except that the pentane of isopentane (gas type &amp;: 8 ft., product name: ISOBUTANE) was carried out, and storage and preliminary foaming were carried out. The foaming molding system was carried out in the same manner as in the above, d), e) and f). The various measurement results are shown in Table 1. Comparative Example 4 The production of the polyethylene-modified styrene-based resin particles was carried out in the same manner as in the example), and the water content adjustment was carried out in the same manner as in the example b) except that the drying time was 丨hour. The impregnation of the foaming agent is carried out by using 1500 g of pentane containing 97% or more of isopentane (gas type 3: 8 ft., manufactured under the name of ISOBUTANE) and raising the temperature by 5 ° C and stirring at this temperature 2 The same procedure as in the case of c) (dry immersion method) of Example 5 was carried out, and the storage system was carried out in the same manner as in the step d) of Example 1. However, when the preliminary foaming is carried out in the same manner as in the case of e) of the first embodiment, foaming of a predetermined multiple is not possible. The results of various measurements are shown in Table 1. Comparative Example 5 The production of the polyethylene-modified stupid vinyl resin particles was carried out in the same manner as in a) of Example 1, and the water content adjustment was carried out in the same manner as in Example ,, except that the impregnation of the foaming agent was Using pentane (gas type b: manufactured by COSMO Petroleum Co., Ltd., product name BUTANE) of 32 〇g n-pentane/isopentane = 75/25 to 85/15, and raising the temperature by 70 ° C and stirring at this temperature for 5 hours In the same manner as in the c) (wet dipping method) of the first embodiment, the storage, the preliminary foaming, and the foam molding were carried out in the same manner as in the example of the example. The results of various measurements are shown in Table 1. Further, the scanned image of the cut surface of the molded body obtained in the same manner as in Example 系 is as shown in Fig. 4 . 30 201037030 Comparative Example 6 « The production of the polyethylene-modified styrene-based resin particles was carried out in the same manner as in Example 1 a), and the water content adjustment was the same as b) of Example 1 except that the drying time was 2 hours. In the case of the immersion of the foaming agent, in addition to 24 〇g of n-pentane/isopentane = 60/40 to 70/30 of pentane (gas type c: manufactured by COSMO Petroleum Co., Ltd., product name COSMOBUTANESILVER), The phantom (wet impregnation method) of Example 1 was carried out in the same manner, and the storage, preliminary foaming, and foaming formation were carried out in the same manner as in d), e) and 〇 of Example 1. The results of these measurements are shown in Table 1. [Table 1] Gas impregnation procedure Gas species added gas amount (% by weight) PE/ PS Modified resin particle water content (ppm) Foamed butterfly particles specified multiple foaming average bubble diameter (D, mm) Bubble diameter standard Deviation (S) Degree of bubble deviation (V=s/O) Water content (ppm) Gas content (ppm) Example 1 Wet a 12 30/70 583 661 8.3 〇0.44 028 0.64〇2 Wet a 13 30/ 70 4320 4056 8.6 〇0.35 0.14 0.43© 3 Wet a 14 40/60 612 748 10.1 〇0.68 0.4 0.590 4 Wet a 14 40/60 4015 3891 9.8 〇0.75 0.15 0.20® 5 Dry a 13 30/70 2331 2178 9.2 〇0.7 02 0.29® 6 Wet b 12 30/70 721 803 8.7 〇0.41 0.31 0.760 Comparative Example 1 Wet a 14 30/70 300 287 10.3 〇0.74 0.84 1.14x 2 Wet a 12 30/70 5526 5703 7.8 〇 0.36 0.33 0.92x 3 Dry a 12 30/70 403 352 8.0 〇0.28 0.24 0·86χ 4 Dry a 10 30/70 1867 1805 7.1 X - - - 5 Wet a 16 30/70 672 650 12.8 〇0.97 135 1.39χ 6 Wet c 12 30/70 1023 1156 9.5 〇0.3 032 1.07χ In the table: Gas type a is the product name ISOBUTANE made by SK Industry Co., Ltd. ( Isoniazid 97% or more) 气体 Gas type b^COSMO company's product name BUTANE (n-pentane / isopentane = 75 / 25 ~ 85 / 15) Gas species c-series COSMO oil company product name COSMO BUTANESILVER (Zhengwuxuan/Xiyan = 60/40~70/30), the specified multiple is 50 times when PE/PS=30/70, and 30 times when 40/60. From Examples 1 to 6 and Comparative Examples 1 to 5, it was found that the foaming compound having a water content of 500 to 5000 ppm and a foaming agent content of 7 · 5 to 11.0% by weight in the modified resin particles 201037030 The resin particles are hardly changed in quality even after long-term storage. Further, from Examples 1 to 6 and Comparative Example 6, it was found that the foaming agent was excellent in firing ratio of butyl baking. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanned image of a cut surface of a molded body obtained in Example 1. Fig. 2 is a scanned image of a cut surface of the molded body obtained in Example 2. Fig. 3 is a scanned image of a cut surface of the molded body obtained in Comparative Example 1. Fig. 4 is a scanned image of a cut surface of the molded body obtained in Comparative Example 5. Fig. 5 is a graph showing the relationship between the ratio (% by weight) of the polystyrene resin and the absorbance ratio (Α698/Α2850). [Main component symbol description] (none) 32

Claims (1)

201037030 VII. Patent application scope: 1 - A long-term storage foaming composite resin particle containing 5 〇〇 5 5 ppm of water in a composite resin of a polyolefin tree and a polystyrene resin 7.5 to 11.0% by weight of pentane. (2) The expandable composite resin particles for long-term storage according to the scope of the invention, wherein the composite resin contains 1 part by weight of a polyethylene resin as a polyolefin resin and 110 to 73 parts by weight of polyphenylene Vinyl resin. Q 3. The expandable composite resin particles for long-term storage according to the first aspect of the invention, wherein the composite resin contains 100 parts by weight of a polyethylene resin as a polyolefin resin and 120 to 560 parts by weight of polystyrene. Resin. 4. The expandable composite resin particle for long-term storage according to the invention of claim 2, wherein the composite resin contains 100 parts by weight of a polyethylene resin as a polyolefin resin and 140 to 450 parts by weight of a polystyrene resin. . 5. The expandable composite resin particles for long-term storage according to the first aspect of the patent application, wherein the water content is 1 to 4500 ppm, and the pentane contained is 8 5 ^ 〜1 〇·〇 weight 0/ Hey. A pre-expanded foamed particle obtained by preliminarily foaming the expandable composite resin particles for long-term storage according to the scope of the patent application. A foamed molded article obtained by in-mold forming preliminary foamed particles of the sixth aspect of the patent application.